Catalysts



Noy. 26, 1 946 H. c. H UFFMAN I 2,411,829

CATALYSTS Filed Aug. 25, 1942 77m Space V/ocxkfy 60 1 a Run Du a a a s a Conversion 7 V INVENTOR. .HAL C.HUFFMAN,

TIORNEY.

. gasoline range lum, tungsten, platinum,

Patented Nov. 26, 1946 uNiTEosrATE-s PATENT OFFICE CATALYSTS Hal 0. Huffman, LongBeach, Calif ass ignor to Union Oil Company oi California, Los Angeles,

Calii'., a corporation of California Application August 25, 1942, Serial No. 456,009 Claims. (Cl. 2 52 211.5)

This invention relates to catalysts and catalytic processes for the processing of various hydrocarbons. More particularly, the invention relates to the catalytic dehydrogenation of light or normally gaseous hydrocarbons such as propane,

butane, isobutane and the like and of commercial naphthas and stocks boiling within the to produce an improved type of motor fuel. This. application is a continuation in part of my copending application Serial No.

' 382,735, filed March 11, 1941.

The principal objects of the invention are to provide an eflicient catalyst which is comparaa long catalytic life,

the saturated to unsaturated hydrocarbons. A more specific object of the invention is to provide a catalyst composition containing a promoterfor the catalytic agent which permits the catalyst to effect a higherdegree of longer period of time. Other and more specific dehydrogenation and for aobjects of the invention will become apparent as the description thereof proceeds.

v The catalytic dehydrogenation of hydrocar-' 'bons is a 'well known process. For this purpose, .many catalytic materials have been employed with varying success. Among these catalysts are the-metal oxides, chromates, sulfates, nitrates, chlorides and other suitable salts of chromium, molybdenum, mium, vanadium, manganese, titanium, tantathorium, uranium, zirconium, tin, copper, etc. Many of these catalysts are effective when supported on such carriers as alumina, magnesium oxide, silica-alumina mixtures, zirconia, titania, thoria, etc. The oxides'of chromium or molybcobalt, nickel, zinc, iron, lead, cad-' columbium, scandium,

beryllium compound. I have found this to be particularly true in the case of chromium oxide or molybdenum oxide or other oxides of metals selected'from the left-hand column of the sixth group of the periodic table distended on activated alumina. A composition of '1 to 10% chromium oxide, 75 to 98% activated alumina and 1 to 15% beryllia has been-found to be a particularly excellent catalyst for dehydrogenating hydrocarbon gases such as normal butane. Preferably, the amount of beryllia should be approximately 5% by weight based uponthe beryl- ]ia, chromium oxide or other oxide and alumina ingredients, although the beryllia content may be lowered to about'2.5% without materially affecting the performance of the catalyst. The invention may perhaps be best understood by reference to the following examples which are merely illustrative of the invention and are no A chromium oxide-alumina catalyst was prepared as follows:

Commercial activated alumina (14-20 mesh) was impregnated with a water solution of chromium' nitrate so that on drying at 400 F. followed by heating in a current of hydrogen at denum distended on alumina arepreferred. For I example, a catalyst composed of 5% chromium oxide and 95% alumina is capable of eifecting' as much as 28-29% conversion of normal butane to butylene at'a temperature of 1050 F. at substantially atmospheric pressure and a space velocity of 15 to'l'l per minute. My invention relates to an improvement in the above process for dehydrogenating hydrocarbons. i

I have discovered that the presence in the catalyst of a small amount of beryllium compound, such as beryllia, not only increases the activity of the foregoing dehydrogenation catalysts to a large extent but maintains the cata-; lytlc life of these catalysts at a high level for a considerably longer using the same catalyst in the absence of the time than in the case of 950 F. a catalyst composition was produced comprising 5% chromium oxide and alumina.

In the above, chromic acid or ammonium di-- chromate may be used in the place of chromium nitrate.

This catalyst was then used to effect dehydrogenation of normal butane at a temperature of about 1050 F. at pressure ofabout atmospheric and at a space velocity of about 15.2 per minute.

As shown in curve No. 1, the conversion of normal butane to butylene was. about 28% 'at the 20 minute point. The catalytic activity gradually tapered oil until at the end of 300 minutes of operation, the conversion wasabout 14.5%. The conversion at the minute point was around Example 2 v Another catalyst was prepared as follows:

Commercial activated alumina was-impregnated with a water solution of beryllium nitrate followed by drying first at 400 F. then at 850 F.

a after which the dried material was treated with tion of normal butane.

' activated structure.

Example 3 Another catalyst was prepared as follows:

Commercial activated alumina (14-20 mesh) was impregnated with a solution of beryllium nitrate and a solution of chromium nitrate in the manner of Example 2 so that on reduction with hydrogen at 950 F. a catalyst composition of 3% chromium oxide, 12% beryllia, and 85% alumine. was obtained.

This catalyst was then used to dehydrogenate normal butane under the same conditions as in the above examples. As shown in curve No. 3,

chromium oxide,

a conversion of about 33% was obtained at the 20 minute point and the conversion gradually decreased to 23% at the end of 300 minutes. At the 150 minute point the conversion was around 27.528%.

It will be noted from a comparison of curves 2 and 3, that while the catalyst used in Example 2 showed a higher lnitialconversion than that used in Example 3, the catalytic activity of the latter is maintained at a higher level to the end of the run. It will be noted also that the presence of beryllia during the reaction materially promotes the activity of the chromium oxide-alu mina catalyst to such extent as to result in a conversion at a high level for a longer period of time. This effect is definitely beneficial since it permits a greater conversion for the same period of reaction time as compared with the unpromoted catalyst or permits the use of the catalyst for a longer period of time before regeneration is required.

The effect of the beryllia is apparently one of true promotion of the catalyst as distinguished from the use of the substance as a catalyst per se. Beryllia when used alone as a catalyst under the foregoing described conditions of operation r showed no ability to catalyze the dehydrogena- A catalyst consisting of 20% beryllia and Q% alumina also showed no catalytic activity to dehydrogenate normal butane.

While the conversion has been illustrated using chromim oxide-alumina as the catalyst and beryllia as the promoter, it is within the spirit of my invention to use beryllia' for the promotion of other dehydrogenationcatalysts such as mentioned above. I prefer, however, to use those catalysts which have been distended on such supports as alumina, magnesium oxide, activated carbon and the like. beryllia as the promoter, other berylliiun compounds such as the sulfate or the nitrate may be used to promote the catalyzing efiect of the dehydrogenation catalysts.

The catalyst composition should preferably be free from metallic halides, particularly metallic fluorides, such as sodium fluoride, since the presence of the metallic halides tends to flux the catalyst in such manner as to cause it to lose its The amount of halides resent in the catalyst should be less than 0.2%

As shown in curve and preferably less than 0.001%. A suitable commercial activated alumina isone prepared and sold commercially by the Aluminum Ore Company of St. Louis, Missouri, under as grade :cF-l. This alumina and chemically pure reagents dissolved in distilled water were used in the foregoing examples. a

The catalysts are preferably prepared by adsorption or impregnation of pilled, pelleted, ex-

Also, instead 01 using truded or otherwise shaped alumina as well as from granular or powdered alumina. In order to distend the beryllia' and the oxide of a metal selected from the left-hand column of the sixth group of the periodic table, it is preferable to employ an aqueous solution of a suitable salt of the metal. In the case of beryllia, Be(NO3)z.3'H2O or BeSOulHzO may be used and in the case of the chromium oxide, ClOa, (NH4): CI'O'I or may be employed. It is preferable to form the chromium sesquioxide on the alumina. These areimpregnated in the alumina and then dried, preferably at two temperature levels. The primary drying is eifected at a lower-[temperature 0f the order of 400500 F. and the final drying is accomplished at a higher calcining temperature between approximately 750 and 1000 F. and even higher in those cases where the catalyst is employed at higher temperatures, with or with out hydrogen or other reducing agent being present. The calcination or heating at such higher temperatures results in reducing the salt to the corresponding oxide. The impregnation may be carried out by immersing the alumina to be impregnated in a solution of known strength of the desiredsalts which is followed by sucking the impregnated material to near dryness such as occurs when placing the impregnated material in a Biichner funnel and connecting the bottom of the funnel. to'a source of vacuum. If desired, the volume of the impregnating solution or solutions may be adjusted so that practically all is adsorbed by the alumina.

Itis preferable to distend first one of the oxides on the alumina and then the other as illustrated in Example 2, thus using separate solutions of the beryllium and chromium or other salts with drying and calcining between impregnations. The alumina is preferably impregnated with the beryllium salt followed by calcination to bring about an efiective intimate combination of the beryllia and alumina before the catalytic material is applied. However, simultaneous deposition from a single water solution of the beryllium salt and the salt of the desired element of the leftehand column of the sixth group of the periodic table is satisfactory, particularly when an impregnating solution of beryllium and chromium or other metal nitrates is used. The drying and calcining is accomplished in, the manner described above.

In some instances, it has been found that an already prepared catalyst consisting of an oxide material and drying. The dried worms may be used as such or they maybe ground to a powder,

mixed with a suitable organic lubricant, such as rosin, stearic acid or other solid fatty acids and then pilled or pelleted. The organic lubricant is removed by passing air through the pilled catalyst at 900-1500 F. If desired, the granular activated alumina" may be mixed with a precipitated hydrous gel of beryllia and the mixture dried and calcined to yield a material which may be powdered, granuled or pilled followed by impregnation with the desired metal oxide producing salt of the left-hand column of the sixth group of the periodic table or the catalytic agent may be added to the wet mixture or activated alumina and precipitated hydrous oxide of beryllium and the mixture then dried and calclined.

If desired, the activated alumina" may be diluted with to.50% of clays or other fillers which thus lowers the cost of the finished cata= lyst. In some cases, the clay is useful as a binder in the catalytic composition.

Also, instead of using the catalystgfor dehyterm "dehydrogenation as used herein is intended to, include the dehydrogenation of not bemade by those skilled in the art without departing from the scope of the claims or the spirit 7 thereof.

I claim;

1. A catalyst consisting of approximately 1 to 15% beryllia, approximately 1 to 1@% of an oxide of a metal selected mm the left-hand column of the sixth group of the periodic table and the remainder an "activated alumina."

2. A catalyst according to claim 1 in which the oxide of the metal selected from the lefthand column of the sixth group of the, periodic table is chromium oxide.

3. A catalyst according to claim 1 in which the oxide of the metal selected irom the lefthand column of the sixth group of the periodic table is molybdenum oxide.

d. A catalyst consisting of approximately 5% beryliia, approximately 5% of an oxide of a metal selected from the left-hand column or the sixth group of the periodic table and the remainder a carrier.

5. A catalyst consisting of approximately 5% beryllia, approximately 5% of chromium oxide and the remainder an activated alumina carrier.

' 1.. a: c, 32o I 

